CN113603840B - Preparation method of rust-proof slow-release polycarboxylic acid superplasticizer - Google Patents
Preparation method of rust-proof slow-release polycarboxylic acid superplasticizer Download PDFInfo
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Abstract
The invention discloses a preparation method of an antirust sustained-release polycarboxylic acid superplasticizer, which comprises the following steps: (1) preparing a special monomer intermediate; (2) preparing a special monomer; (3) and (3) synthesizing the rust-proof slow-release polycarboxylic acid superplasticizer. The preparation method of the invention is that citraconic anhydride is taken as an initiator, and is ring-opening polymerized with epoxybutane to generate citraconic anhydride polybutylene glycol ester special monomer intermediate, alcohol amine is grafted at the tail end of the special monomer intermediate to prepare alcohol amine end-capped special monomer, and then the special monomer, acrylic acid, carboxylic ester and polyether macromonomer are adopted to synthesize the rust-proof slow-release polycarboxylic acid superplasticizer.
Description
Technical Field
The invention belongs to the technical field of synthesis of polycarboxylic acid superplasticizer, and in particular relates to a preparation method of rust-proof slow-release polycarboxylic acid superplasticizer.
Background
Under the large background that the concrete industry in China rapidly develops and the urban and rural integrated process is continuously accelerated, the performance of the concrete material is developing towards the directions of high durability, high strength and strong adaptability. Polycarboxylic acid superplasticizers are widely used as additives in concrete materials, and their functionality is one of the important factors determining the properties of the concrete materials.
The research at present finds that the corrosion of sulfate and chloride can cause the problems of expansion cracking, steel bar corrosion, strength loss and the like of the reinforced concrete structure. Especially steel bar corrosion can severely reduce the service life of the building. The common concrete rust and corrosion inhibition measures mainly comprise three types: (1) properly reducing the water-cement ratio and improving the strength grade of the concrete; (2) the high-efficiency sulfate-resistant cement is used; (3) the anti-rust corrosion-inhibition paint is used for coating the surface of the concrete structure. However, these three rust and corrosion inhibition measures have respective disadvantages: the measure (1) improves the construction cost of the project; the sulfate-resistant cement manufacturers in the measure (2) are less; the construction difficulty of the measure (3) is high, and the coating is easy to fall off. On the other hand, when the existing polycarboxylic acid superplasticizer is added into concrete with high mud content and poor grading aggregate, the problems of poor concrete fluidity, difficult site construction and the like still exist under the conditions of high temperature, drying, long-distance transportation and the like due to the fact that the concrete slump and expansion loss are too fast.
Disclosure of Invention
The invention aims to provide a preparation method of an antirust sustained-release polycarboxylic acid superplasticizer, which can effectively overcome many defects of the existing polycarboxylic acid superplasticizer.
The invention adopts the technical scheme that: the preparation method comprises the following steps:
(1) preparation of a special monomer intermediate: preheating and melting citraconic anhydride, adding the citraconic anhydride into a reaction kettle, and adding a proper amount of alkali metal catalyst and cocatalyst hole ether [2, 2]; 3-4 times of replacement under the nitrogen atmosphere of the sealing kettle; heating the reaction kettle to maintain the temperature at 125-130 ℃, and introducing a proper amount of epoxybutane, wherein the pressure in the kettle is kept not higher than 0.05MPa for preliminary initiation reaction, and the initiation amount of epoxybutane is 3-6% of the total feeding amount; heating continuously after the reaction is completely initiated, controlling the temperature of the kettle to be 130-135 ℃, controlling the pressure of the kettle to be not higher than 0.07MPa, feeding the residual epoxybutane raw material completely, and aging for 2 hours after the feeding is completed; and (3) after aging, degassing and neutralizing to obtain the special monomer intermediate.
(2) Preparation of special monomers: adding the special monomer intermediate into a reaction kettle, and adding a Lewis acid catalyst; sealing the kettle, replacing 3-4 times by using nitrogen atmosphere, keeping the kettle temperature at 50-60 ℃, and dripping epoxy chloropropane and the bottom material to perform ring-opening reaction for 2-4 hours; after the reaction is completed, alcohol amine is added under the protection of nitrogen, and the temperature is maintained at 60-70 ℃ for reaction for 3-5 hours, so that the special monomer is obtained.
(3) And (3) synthesizing an antirust slow-release polycarboxylic acid superplasticizer: sequentially adding polyether macromonomer and deionized water into a container, and stirring until the polyether macromonomer and the deionized water are dissolved; preparing a first material: dissolving a certain amount of special monomer, acrylic acid and carboxylic ester in deionized water; preparing a material B: dissolving a certain amount of mercaptoethanol and ferrous sulfate in deionized water; adding a certain amount of tert-butyl hydroperoxide into a container, stirring for 2-4 min, and then beginning to dropwise add the materials A and B simultaneously; the dripping time of the materials A and B is 1-2 hours, and the temperature is kept for reaction for 1-2 hours after the dripping is finished; cooling after the reaction is completed, adding 20% potassium hydroxide solution into the bottle to adjust the pH value to be neutral, and obtaining the rust-proof slow-release polycarboxylic acid superplasticizer.
The alkali metal catalyst in the step (1) is one or more of sodium metal, sodium oxide, sodium peroxide, sodium hydride and sodium hydroxide, and the dosage of the alkali metal catalyst is 0.5-2 per mill of the total feeding amount; the consumption of the cocatalyst hole ether [2, 2] is 1-4 per mill of the total feeding amount.
The mass ratio of the citraconic anhydride to the epoxybutane in the step (1) is 1:2-4, preferably 1:2-3.
The degassing time in the step (1) is 30-100 min, the temperature is 80-110 ℃, the preferred degassing time is 40-75 min, and the temperature is 90-105 ℃.
The neutralization time in the step (1) is 10-60 min, the temperature is 60-85 ℃, the neutralization time is 25-45 min, and the temperature is 65-80 ℃.
The acid used in the neutralization in the step (1) is one or more of citric acid, oxalic acid, glycolic acid, glacial acetic acid and sulfamic acid, and the pH value of the system after neutralization is 5.5-7.0.
The molecular weight of the third monomer intermediate in the step (1) is 350 to 550, preferably 400 to 500.
The molar ratio of the special monomer intermediate to the epichlorohydrin to the alcohol amine in the step (2) is 1:1.1:1.12.
The Lewis acid catalyst in the step (2) is one or more of boron trifluoride diethyl etherate, indium trichloride, stannic chloride and zinc dichloride, and the dosage is 0.4-1.0% of the total mass of reactants in the step (2), preferably 0.5-0.8%.
The alcohol amine in the step (2) is one or more of monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine and monoethanol-monoisopropanolamine.
The polyether macromonomer in the step (3) is one or more of polyethylene glycol monomethyl ether methyl butenoate, polyethylene glycol monomethyl ether methacrylate and polyethylene glycol monomethyl ether acrylate, and the molecular weight is 3000-4000.
The carboxylic acid ester in the step (3) is one or more of diethyl maleate, dimethyl itaconate, methyl acrylate, butyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
In the step (3), the dosage of ferrous sulfate is 0.15-0.25% of the mass of the polyether macromonomer, the dosage of mercaptoethanol is 0.3-0.4% of the mass of the polyether macromonomer, and the dosage of tert-butyl hydroperoxide is 2.0-4.0% of the mass of the polyether macromonomer.
In the step (3), the molar ratio of the acrylic acid to the carboxylic ester to the special monomer to the polyether macromonomer is 2:1:3:2.
The solid content of the rust-proof slow-release polycarboxylic acid superplasticizer obtained in the step (3) is 50-70%.
The preparation method of the invention is that citraconic anhydride is taken as an initiator, and is ring-opening polymerized with epoxybutane to generate citraconic anhydride polybutylene glycol ester special monomer intermediate, alcohol amine is grafted at the tail end of the special monomer intermediate to prepare alcohol amine end-capped special monomer, and then the special monomer, acrylic acid, carboxylic ester and polyether macromonomer are adopted to synthesize the rust-proof slow-release polycarboxylic acid superplasticizer.
Because of the existence of the alcohol amine end-capped structure in the special monomer, on one hand, the unshared electron pair of nitrogen atoms in the alcohol amine is mutually adsorbed with the surfaces of the steel bars and oxides thereof to form an adsorption film which can play a role in blocking, so that the charge state and interface property of the surfaces of the steel bars are changed, the charge transfer resistance of the surfaces of the steel bars is increased, and the initial corrosion rate of the steel bars in concrete is reduced; on the other hand, the adsorbed nonpolar group on the alcohol amine end-capped structure forms a hydrophobic protective film on the surface of the reinforced concrete, thereby preventing the migration of charges and substances related to corrosion reaction, inhibiting the further corrosion of the reinforced concrete and improving the overall rust resistance of the reinforced concrete. Meanwhile, in the process of synthesizing the rust-proof slow-release polycarboxylic acid superplasticizer, along with the introduction of carboxylic ester and partial substitution of carboxylic groups with anchoring effect in common technology, the charge density on the molecular main chain of the polycarboxylic acid superplasticizer can be reduced, and the adsorption rate of the polycarboxylic acid superplasticizer on the surface of cement particles is inhibited, so that the polycarboxylic acid superplasticizer has the dispersing effect and slow-release function.
The invention has the advantages that:
1. the invention adopts citraconic anhydride and epoxybutane to prepare the special monomer intermediate under the catalysis of alkali metal catalyst and cave ether [2, 2], and improves the reaction efficiency and reduces the residue of epoxide by introducing the cave ether [2, 2] which is a phase transfer catalyst with better synergistic effect with the alkali metal catalyst.
2. Compared with the traditional catalytic system, the Lewis acid catalytic system introduced in the synthesis process of the special monomer has higher selectivity and fewer byproducts, and meanwhile, the alcohol amine is used for blocking the monomer, so that the novel antirust and corrosion inhibition functions are given to the monomer.
3. According to the invention, the rust-proof slow-release polycarboxylic acid superplasticizer is synthesized by adopting special monomers, acrylic acid, carboxylic ester and polyether macromonomer, and on the basis of maintaining the basic performance of the common polycarboxylic acid superplasticizer, the charge density of a molecular main chain of the superplasticizer is reduced along with the introduction of the carboxylic ester, the adsorption rate on the surface of cement particles is inhibited, and the release rate in the hydration process of cement paste is slow, so that a new slow-release slump retaining effect is obtained.
4. The preparation method provided by the invention has the advantages of reasonable process, simple operation, high reaction efficiency, less reaction residue and excellent product application performance, and further enhances the functionality of the polycarboxylic acid superplasticizer, thereby laying a foundation for wider application.
Detailed Description
Example 1:
(1) preparation of a special monomer intermediate: 120g of citraconic anhydride is preheated and melted and then added into a reaction kettle, and then 0.29g of sodium hydride and 0.71g of promoter hole ether [2, 2] are added; 3 times of replacement under the nitrogen atmosphere of the sealing kettle; heating the reaction kettle, maintaining the temperature at 125-130 ℃, introducing 14g of butylene oxide, and keeping the pressure in the kettle not higher than 0.05MPa for preliminary initiation reaction; heating continuously after the reaction is completely initiated, controlling the temperature of the kettle to be 130-135 ℃, controlling the pressure of the kettle to be not higher than 0.07MPa, and aging for 2 hours after finishing feeding 402g of the residual butylene oxide raw material; after aging, 536g of special monomer intermediate with molecular weight of 500 and pH value of 6.1 is obtained by degassing and adding 2.3g of citric acid for neutralization.
(2) Preparation of special monomers: 400g of the intermediate obtained in the step (1) is added into a reaction kettle, and 2.7g of Lewis acid catalyst boron trichloride diethyl ether is added; sealing the kettle, replacing for 3 times by using nitrogen atmosphere, dropwise adding 81g of epichlorohydrin and a substrate at the temperature of 50-60 ℃ to perform ring-opening reaction for 3 hours; 59g of monoethanolamine is added under the protection of nitrogen after the reaction is completed, and the reaction is carried out for 2 hours at the temperature of 60-70 ℃ to obtain 540g of special monomer.
(3) And (3) synthesizing an antirust slow-release polycarboxylic acid superplasticizer: 300g of polyethylene glycol monomethyl ether methyl butenoate with molecular weight of 3000 and 200g of deionized water are sequentially added into a four-neck flask and stirred until the polyethylene glycol monomethyl ether methyl butenoate is dissolved. Preparing a first material: 98g of special monomer, 7.2g of acrylic acid and 8.6g of diethyl maleate are taken and dissolved in 200g of deionized water. Preparing a material B: 1.23g of mercaptoethanol and 0.62g of ferrous sulfate are taken and dissolved in 24g of deionized water. 8.2g of t-butyl hydroperoxide was added to the flask, and after stirring for 2 minutes, the first and second materials were simultaneously added dropwise. Dripping the materials A and B for 1h, and keeping the temperature for reaction for 1h after dripping; after the reaction is completed, cooling, adding 20% potassium hydroxide solution into the bottle to adjust the pH value to be neutral, and obtaining 848g of antirust slow-release polycarboxylate superplasticizer with the solid content of 50%.
Example 2:
(1) preparation of a special monomer intermediate: 130g of citraconic anhydride is preheated and melted and then added into a reaction kettle, and then 0.49g of catalyst metal sodium and 1.86g of promoter hole ether [2, 2] are added; 3 times of replacement under the nitrogen atmosphere of the sealing kettle; heating the reaction kettle, maintaining the temperature at 125-130 ℃, introducing 11g of butylene oxide, and keeping the pressure in the kettle not higher than 0.05MPa for preliminary initiation reaction; continuously heating after the reaction is completely initiated, controlling the kettle temperature to be 130-135 ℃, controlling the kettle pressure to be not higher than 0.07MPa, and aging for 2 hours after finishing the feeding of 346g of residual butylene oxide raw material; after aging, 487g of a special monomer intermediate with a molecular weight of 420 and a pH value of 6.0 is obtained by degassing and adding 1.55g of glycolic acid for neutralization.
(2) Preparation of special monomers: 350g of the intermediate obtained in the step (1) is added into a reaction kettle, and 3.7g of Lewis acid catalyst tin tetrachloride is added; sealing the kettle, replacing for 3 times by using nitrogen atmosphere, dropwise adding 85g of epoxy chloropropane at 50-60 ℃ and performing ring-opening reaction with a substrate for 2.5h; after the reaction is completed, 98g of isopropanolamine is added under the protection of nitrogen, and the reaction is carried out for 3 hours at the temperature of 60-70 ℃ to obtain 533g of special monomer.
(3) And (3) synthesizing an antirust slow-release polycarboxylic acid superplasticizer: 400g of polyethylene glycol monomethyl ether acrylate with molecular weight of 4000 and 100g of deionized water are sequentially added into a four-neck flask and stirred until the mixture is dissolved. Preparing a first material: 88g of special monomer, 7.2g of acrylic acid and 7.9 g of dimethyl itaconate are taken and dissolved in 100g of deionized water. Preparing a material B: 1.5g of mercaptoethanol and 0.9g of ferrous sulfate are taken and dissolved in 27g of deionized water. To the flask, 12g of t-butyl hydroperoxide was added, and after stirring for 2 minutes, the first and second materials were simultaneously added dropwise. Dripping the materials A and B for 2 hours, and keeping the temperature for reaction for 1.5 hours after dripping; after the reaction is completed, cooling, adding 20% potassium hydroxide solution into the bottle to adjust the pH value to be neutral, and obtaining 739g of antirust slow-release polycarboxylic acid superplasticizer with the solid content of 70%.
Example 3:
(1) preparation of a special monomer intermediate: 150g of citraconic anhydride is preheated and melted and then added into a reaction kettle, and then 0.66g of catalyst sodium hydroxide and 1.85g of promoter cave ether [2, 2] are added; 4 times of replacement under the nitrogen atmosphere of the sealing kettle; heating the reaction kettle, maintaining the temperature at 125-130 ℃, introducing 21g of epoxybutane, and keeping the pressure in the kettle not higher than 0.05MPa for preliminary initiation reaction; continuously heating after the reaction is completely initiated, controlling the temperature of the kettle to be 130-135 ℃, controlling the pressure of the kettle to be not higher than 0.07MPa, and aging for 2 hours after finishing feeding 432g of the residual butylene oxide raw material; after aging, the mixture was degassed and neutralized by adding 2.47g oxalic acid to obtain 603g of a specific monomer intermediate having a molecular weight of 450 and a pH of 6.5.
(2) Preparation of special monomers: 360g of the intermediate obtained in the step (1) is added into a reaction kettle, and 3.2g of Lewis acid catalyst indium trichloride is added; sealing the kettle, replacing for 3 times by using nitrogen atmosphere, dropwise adding 81g of epichlorohydrin and a substrate at the temperature of 50-60 ℃ to perform ring-opening reaction for 3.5h; after the reaction is completed, 94g of diethanolamine is added under the protection of nitrogen, and the reaction is carried out for 3.5 hours at the temperature of 60-70 ℃ to obtain 535g of special monomer.
(3) And (3) synthesizing an antirust slow-release polycarboxylic acid superplasticizer: 350g of polyethylene glycol monomethyl ether acrylate with molecular weight of 3500 and 200g of deionized water are sequentially added into a four-neck flask and stirred until the mixture is dissolved. Preparing a first material: 100g of special monomer, 7.2g of acrylic acid and 7.2g of dimethyl maleate are taken and dissolved in 100g of deionized water. Preparing a material B: 1.2g of mercaptoethanol and 0.7g of ferrous sulfate are taken and dissolved in 21g of deionized water. To the flask, 12.25g of t-butyl hydroperoxide was added, and after stirring for 4 minutes, the first and second materials were simultaneously added dropwise. Dripping the materials A and B for 1h, and keeping the temperature for reaction for 1.5h after dripping; after the reaction is completed, cooling, adding 20% potassium hydroxide solution into the bottle to adjust the pH value to be neutral, and obtaining 796g of antirust slow-release polycarboxylic acid superplasticizer with the solid content of 60%.
Example 4:
(1) preparation of a special monomer intermediate: 125g of citraconic anhydride is preheated and melted and then added into a reaction kettle, and then 0.35g of sodium oxide as a catalyst and 0.68g of hole ether as a cocatalyst [2, 2] are added; 3 times of replacement under the nitrogen atmosphere of the sealing kettle; heating the reaction kettle, maintaining the temperature at 125-130 ℃, introducing 16g of butylene oxide, and keeping the pressure in the kettle not higher than 0.05MPa for preliminary initiation reaction; continuously heating after the reaction is completely initiated, controlling the temperature of the kettle to be 130-135 ℃, controlling the pressure of the kettle to be not higher than 0.07MPa, and aging for 2 hours after finishing feeding the residual 350g of butylene oxide raw material; after aging, 491g of special monomer intermediate with molecular weight of 440 and pH value of 5.9 is obtained by degassing and adding 1.42g of sulfamic acid for neutralization.
(2) Preparation of special monomers: adding 380g of the intermediate obtained in the step (1) into a reaction kettle, and adding 2.7g of Lewis acid catalyst boron trichloride diethyl ether; sealing the kettle, replacing for 4 times by using nitrogen atmosphere, dropwise adding 87g of epoxy chloropropane at the temperature of 50-60 ℃ and performing ring-opening reaction with a substrate for 4 hours; 129g of diisopropanolamine is added under the protection of nitrogen after the reaction is completed, and the reaction is carried out for 3.5 hours at the temperature of 60-70 ℃ to obtain 596g of special monomer.
(3) And (3) synthesizing an antirust slow-release polycarboxylic acid superplasticizer: 370g of polyethylene glycol monomethyl ether methyl butenoate with a molecular weight of 3700 and 210g of deionized water are sequentially added into a four-necked flask and stirred until the mixture is dissolved. Preparing a first material: 100g of special monomer, 7.2g of acrylic acid and 6.4 of butyl acrylate are taken and dissolved in 160g of deionized water. Preparing a material B: 1.13g of mercaptoethanol and 0.55g of ferrous sulfate are taken and dissolved in 38g of deionized water. To the flask, 12.1g of t-butyl hydroperoxide was added, and after stirring for 4 minutes, the first and second materials were simultaneously added dropwise. Dripping the materials A and B for 1.5h, and keeping the temperature for reaction for 2h after the dripping is finished; after the reaction is completed, cooling, adding 20% potassium hydroxide solution into the bottle to adjust the pH value to be neutral, and obtaining 902g of rust-proof slow-release polycarboxylic acid superplasticizer with the solid content of 55%.
Example 5:
(1) preparation of a special monomer intermediate: 170g of citraconic anhydride is preheated and melted and then added into a reaction kettle, and then 0.73g of catalyst sodium hydroxide and 1.69g of promoter cave ether [2, 2] are added; 4 times of replacement under the nitrogen atmosphere of the sealing kettle; heating the reaction kettle, maintaining the temperature at 125-130 ℃, introducing 24g of butylene oxide, and keeping the pressure in the kettle not higher than 0.05MPa for preliminary initiation reaction; after the reaction is completely initiated, continuing to heat, controlling the temperature of the kettle to be 130-135 ℃, controlling the pressure of the kettle to be not higher than 0.07MPa, and aging for 2 hours after finishing feeding the 550g of the residual butylene oxide raw material; after aging, 744g of a special monomer intermediate having a molecular weight of 490 and a pH of 6.8 was obtained by degassing and neutralizing with 5.96g of glacial acetic acid.
(2) Preparation of special monomers: adding 510g of the intermediate obtained in the step (1) into a reaction kettle, and adding 5.7g of Lewis acid catalyst zinc dichloride; sealing the kettle, replacing for 3 times by using nitrogen atmosphere, dropwise adding 105g of epoxy chloropropane with a substrate at the temperature of 50-60 ℃ to perform ring-opening reaction for 4 hours; 136g of monoethanol-isopropanolamine is added under the protection of nitrogen after the reaction is completed, and the reaction is carried out for 3 hours at the temperature of 60-70 ℃ to obtain 751g of special monomer.
(3) And (3) synthesizing an antirust slow-release polycarboxylic acid superplasticizer: 335g of polyethylene glycol monomethyl ether methacrylate with molecular weight of 3350 and 140g of deionized water are sequentially added into a four-necked flask and stirred until dissolved. Preparing a first material: 105g of special monomer, 7.2g of acrylic acid and 6.5g of hydroxypropyl acrylate are taken and dissolved in 100g of deionized water. Preparing a material B: 1.24g of mercaptoethanol and 0.57g of ferrous sulfate are taken and dissolved in 35g of deionized water. 9.38g of t-butyl hydroperoxide was added to the flask, and after stirring for 3 minutes, the first and second materials were simultaneously added dropwise. Dripping the materials A and B for 1h, and keeping the temperature for reaction for 1.5h after dripping; after the reaction is completed, cooling, adding 20% potassium hydroxide solution into the bottle to adjust the pH value to be neutral, and obtaining 736g of rust-proof slow-release polycarboxylic acid superplasticizer with the solid content of 63%.
Claims (8)
1. The preparation method of the rust-proof slow-release polycarboxylic acid superplasticizer comprises the following steps:
(1) preparation of a special monomer intermediate: preheating and melting citraconic anhydride, adding the citraconic anhydride into a reaction kettle, and adding a proper amount of alkali metal catalyst and cocatalyst hole ether [2, 2]; 3-4 times of replacement under the nitrogen atmosphere of the sealing kettle; heating the reaction kettle to maintain the temperature at 125-130 ℃, and introducing a proper amount of epoxybutane, wherein the pressure in the kettle is kept not higher than 0.05MPa for preliminary initiation reaction, and the initiation amount of epoxybutane is 3-6% of the total feeding amount; heating continuously after the reaction is completely initiated, controlling the temperature of the kettle to be 130-135 ℃, controlling the pressure of the kettle to be not higher than 0.07MPa, feeding the residual epoxybutane raw material completely, and aging for 2 hours after the feeding is completed; the special monomer intermediate is prepared by degassing and neutralizing after aging;
(2) preparation of special monomers: adding the special monomer intermediate into a reaction kettle, and adding a Lewis acid catalyst; sealing the kettle, replacing 3-4 times by using nitrogen atmosphere, keeping the kettle temperature at 50-60 ℃, and dripping epoxy chloropropane and the bottom material to perform ring-opening reaction for 2-4 hours; after the reaction is completed, under the protection of nitrogen, alcohol amine is added to maintain the temperature of 60-70 ℃ for reaction for 3-5 hours, so that the special monomer is obtained; the Lewis acid catalyst is one or more of boron trifluoride diethyl etherate, indium trichloride, stannic chloride and zinc dichloride, and the dosage of the Lewis acid catalyst is 0.4-1.0% of the total mass of reactants in the step;
(3) and (3) synthesizing an antirust slow-release polycarboxylic acid superplasticizer: sequentially adding polyether macromonomer and deionized water into a container, and stirring until the polyether macromonomer and the deionized water are dissolved; preparing a first material: dissolving a certain amount of special monomer, acrylic acid and carboxylic ester in deionized water; preparing a material B: dissolving a certain amount of mercaptoethanol and ferrous sulfate in deionized water; adding a certain amount of tert-butyl hydroperoxide into a container, stirring for 2-4 min, and then beginning to dropwise add the materials A and B simultaneously; the dripping time of the materials A and B is 1-2 hours, and the temperature is kept for reaction for 1-2 hours after the dripping is finished; cooling after the reaction is completed, adding 20% potassium hydroxide solution into the bottle to adjust the pH value to be neutral, and obtaining the rust-proof slow-release polycarboxylic acid superplasticizer; the carboxylic acid ester is one or more of diethyl maleate, dimethyl itaconate, methyl acrylate, butyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
2. The method for preparing the rust-preventive slow-release polycarboxylic acid superplasticizer, which is characterized by comprising the following steps of: the alkali metal catalyst in the step (1) is one or more of sodium metal, sodium oxide, sodium peroxide, sodium hydride and sodium hydroxide, and the dosage of the alkali metal catalyst is 0.5-2 per mill of the total feeding amount; the consumption of the cocatalyst hole ether [2, 2] is 1-4 per mill of the total feeding amount.
3. The method for preparing the rust-preventive slow-release polycarboxylic acid superplasticizer, which is characterized by comprising the following steps of: the mass ratio of the citraconic anhydride to the epoxybutane in the step (1) is 1:2-4.
4. The method for preparing the rust-preventive slow-release polycarboxylic acid superplasticizer, which is characterized by comprising the following steps of: the acid used in the neutralization in the step (1) is one or more of citric acid, oxalic acid, glycolic acid, glacial acetic acid and sulfamic acid, and the pH value of the system after the neutralization is 5.5-7.0.
5. The method for preparing the rust-preventive slow-release polycarboxylic acid superplasticizer, which is characterized by comprising the following steps of: the molar ratio of the special monomer intermediate to the epichlorohydrin to the alcohol amine in the step (2) is 1:1.1:1.12.
6. The method for preparing the rust-preventive slow-release polycarboxylic acid superplasticizer, which is characterized by comprising the following steps of: the alcohol amine in the step (2) is one or more of monoethanolamine, diethanolamine, monoisopropanolamine and diisopropanolamine.
7. The method for preparing the rust-preventive slow-release polycarboxylic acid superplasticizer, which is characterized by comprising the following steps of: the polyether macromonomer in the step (3) is one or more of polyethylene glycol monomethyl ether methyl butenoate, polyethylene glycol monomethyl ether methacrylate and polyethylene glycol monomethyl ether acrylate, and the molecular weight is 3000-4000.
8. The method for preparing the rust-preventive slow-release polycarboxylic acid superplasticizer, which is characterized by comprising the following steps of: the dosage of ferrous sulfate in the step (3) is 0.15-0.25% of the mass of the polyether macromonomer, the dosage of mercaptoethanol is 0.3-0.4% of the mass of the polyether macromonomer, and the dosage of tert-butyl hydroperoxide is 2.0-4.0% of the mass of the polyether macromonomer; the molar ratio of the acrylic acid to the carboxylic ester to the special monomer to the polyether macromonomer is 2:1:3:2.
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